Applied Energy 178 (2016) 616–623

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Preparation and characterization of capric-myristic-stearic acid eutectic

mixture/modified expanded vermiculite composite as a form-stable
phase change material
Haiting Wei, Xiuzhen Xie, Xiangqi Li ⇑, Xingshui Lin
Institute of Materials Science and Engineering, Fuzhou University, Fuzhou 350180, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The expanded vermiculite/carbon

(EVC) was obtained by in-situ
carbonizing CTAB.

The acid treated EVC (aEVC) was an
optimum CA-MA-SA supporting
matrix.

The melting latent heat of the CA-MA-
SA/aEVC was 86.4 J/g at 22.92 °C.

The thermal conductivity of CA-MA-
SA/aEVC was 0.667 W/mK.

The CA-MA-SA/aEVC composite PCM
has good thermal and chemical
stabilities.

a r t i c l e i n f o a b s t r a c t

Article history: A novel capric-myristic-stearic acid (CA-MA-SA)/modified expanded vermiculite composite phase change
Received 12 March 2016 material (PCM) with simultaneously enhanced thermal conductivity and latent heat was prepared in this
Received in revised form 4 June 2016 study. The expanded vermiculite/carbon composite (EVC), obtained by in-situ carbonizing cetyl trimethyl
Accepted 18 June 2016
ammonium bromide in the layer of expanded vermiculite, was treated with nitric acid (aEVC) to be used as
the CA-MA-SA supporting matrix. The results showed that the thermal conductivity of CA-MA-SA/aEVC was
greatly enhanced by introducing carbon and the CA-MA-SA adsorption capacity was improved by the
Keywords:
acid-treatment of EVC. The thermal conductivity of CA-MA-SA/aEVC was 0.667 W/mK, which was 31.6%
Expanded vermiculite
Capric-myristic-stearic acid
higher than that of CA-MA-SA/expanded vermiculite (EV). The latent heats of the CA-MA-SA/aEVC were
Carbonize 86.4 J/g at the melting temperature of 22.92 °C and 80.43 J/g at the freezing temperature of 21.03 °C, which
Acid treatment were also greatly higher than those of CA-MA-SA/EV. The results of the thermo-gravimetric analysis (TGA),
Form-stable composite PCM thermal cycling test and Fourier transform infrared spectroscopy (FT-IR) indicated that the CA-MA-SA/aEVC
composite PCM was thermally stable and chemically inert. Thus, the prepared CA-MA-SA/aEVC composite
PCM is a promising material for the building energy efficiency applications.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction

Buildings not only consume enormous amount of energy, but

also cause huge amount of greenhouse gas around the world.
⇑ Corresponding author at: Institute of Materials Science and Engineering, Fuzhou Therefore, energy efficient buildings are recently one of the most
University New Campus, Minhou College Town, Fuzhou, Fujian 350180, China. important issues since both economic and environmental factors
E-mail address: lxiangqi@fzu.edu.cn (X. Li).

http://dx.doi.org/10.1016/j.apenergy.2016.06.109
0306-2619/Ó 2016 Elsevier Ltd. All rights reserved.
 H. Wei et al. / Applied Energy 178 (2016) 616–623 617

nowadays are of great importance in the world [1,2]. Phase change 2. Experimental
materials (PCMs) for latent heat thermal energy storage (LHTES)
have been extensively investigated in building energy conservation 2.1. Materials
applications due to high energy storage density and latent heat
property, small temperature variation form storage to retrieval, Capric acid (CA, C10H20O2, AR), myristic acid (MA, C14H28O2, AR),
and repeatable utilization property [3–6]. stearic acid (SA, C18H36O2, AR), nitric acid (HNO3, AR) and cetyl tri-
Fatty acids are organic PCM with typical solid-to-liquid phase methyl ammonium bromide (CTAB, C19H42BrN, AR) were pur-
change characteristics. They have been recommended as LHTES chased from Sinopharm Chemical Reagent Company. The
due to their high latent heat capacity, good chemical and thermal expanded vermiculite was purchased from Jinli mining industry
stability, little or no supercooling during phase transition, environ- co., Ltd.
ment friendly [7,8]. In practice, fatty acids are impregnated into
porous building materials to prepare form-stable composites. Con- 2.2. Determination of eutectic composition
sidering the strong capillary force generated on a pore with small
diameter [9], a variety of natural porous materials with smaller The eutectic mass ratio of fatty acid mixture can be approxi-
pores such as expanded perlite [10,11], attapulgite [12] and hal- mately calculated via the Schrader equation [26].
loysite [13], are frequently used to avoid the leakage of fatty acids  1
during melting process. Additionally, the low thermal conductivity 1 R ln X A
Tm ¼  ð1Þ
of fatty acids poses a challenge for their applications. In order to TA DH A
solve this problem, the additives with high thermal conductivity,
where Tm is the phase change temperature of the eutectic mixture,
including expanded graphite [14,15], carbon nanotubes [16,17]
TA and DHA are the phase change temperature and latent heat of
and silica fume [18], have been introduced to enhance the thermal
component A, XA is the mole fraction of component A in the mixture,
conductivity of form-stable composites.
and R is the gas constant.
Vermiculite is a layered silicate mineral with 2:1 crystalline
The thermal properties of CA, MA and SA measured by differen-
structure. Layers consist of octahedrally coordinated cations (typi-
tial scanning calorimetry (DSC) are given in Table 1. Through Eq. (1),
cally Mg, Fe and Ti) sandwiched between tetrahedrally coordinated
the theoretical mass ratios of CA-MA, MA-SA, CA-SA eutectic mix-
cations (typically Si and Al). The isomorphous substitution of Si4+ by
tures were firstly calculated, and then the ternary eutectic mass
Al3+ leads to a net negative surface charge that is compensated by
ratio was calculated to be 71.8:23.2:5.0 by regarding the eutectic
interlayer exchangeable hydrated cations (Ca2+, Mg2+, Cu2+ and
mixture of CA-MA as a pseudo-single component [27]. Considering
Na+). These charge balancing inorganic cations can be mutually
the Schrader equation is an approximate calculation formula, the
exchanged or exchanged by organic cations [19]. The vermiculite
mass ratios of the eutectic mixtures need to be verified by experi-
volume can be expanded by several times when heated at high tem-
ments [26]. The mass ratios and melting temperatures of eutectic
perature for a short duration due to the sudden release of interlayer
mixtures measured by DSC are shown in Table 2. The ternary phase
water. This disrupts the structure and forms a highly porous mate-
diagram of CA-MA-SA can be expressed in the form of equilateral
rial named expanded vermiculite. Expanded vermiculite has good
triangle as shown in Fig. 1. The experimental eutectic points of
physical properties, such as fire resistance, the porous structure,
CA-MA, MA-SA and CA-SA are labeled as A, B, and C, respectively.
non-toxicity and low density, and is usually used as a lightweight
Point E, the theoretical eutectic point of CA-MA-SA is located into
aggregate for plaster, concrete compounds and the component of
the small triangle formed by KA, DB and HC. A series of CA-MA-SA
wallboard filler [20]. In recent years, a new application using
mixtures with different mass ratios (CA:MA:SA = 71.8:23.2:5.0;
expanded vermiculite as a PCM supporting matrix has been
71.8:22.5:5.7; 71.8:23.9:4.3; 71.1:23.2:5.7; 72.5:23.2:4.3;
explored. Chung et al. [21] used expanded vermiculite as the
72.5:22.5:5.0; 71.1:23.9:5.0) were prepared and then measured
n-octadecane supporting matrix. Although the prepared composite
by DSC. Among them, the CA-MA-SA with the mass ratio of
PCM was thermally stable and chemically inert, the thermal
72.5:22.5:5.0 has the lowest melting temperature. In order to fur-
conductivity of composite PCM was low (0.1569 W/mK). Karaipekli
ther verify 72.5:22.5:5.0 as the eutectic composition, the mixture
and Sari [22] reported that the thermal conductivities of fatty
was tested by DSC performed at a slow heating rate of 1 °C/min.
acids/expanded vermiculite composite PCMs were increased in
The DSC curve is shown in Fig. 2. As seen from Fig. 2, only one
the range of 104–150% by addition of 10 wt% expanded graphite.
solid–liquid phase change peak was observed, which evidenced
Guan et al. [23] implanted network carbon in vermiculite layers
ternary eutectic forming [28]. The determined eutectic composition
by in-situ carbonizing sucrose to enhance the thermal conductivity
in this work has little difference with the reported value of CA:MA:
of paraffin/expanded vermiculite composite. Though the thermal
SA = 72.65:21.17:6.18 by Ke et al. [26].
conductivity of the composite PCM improved greatly, the latent
heats decreased. The similar results were also reported in the other
2.3. Preparation of CA-MA-SA eutectic mixture
related works [11,24,25]. Therefore, it is necessary to come up with
a method to simultaneously improve the thermal conductivity and
The CA-MA-SA eutectic mixture was prepared by heating-
latent heat of the composite PCM.
ultrasonic method. 7.25 g CA, 2.25 g MA and 0.5 g SA were mixed
In this study, a novel method was proposed to achieve the pur-
uniformly in a sealed beaker followed by melting and blending at
pose. The expanded vermiculite/carbon composite was prepared
70 °C for 40 min. Then the mixtures were cooled to the room tem-
by implanting carbon in layers of expanded vermiculite via in-
perature and conserved under sealed condition.
situ carbonizing cetyl trimethyl ammonium bromide (CTAB). As a
cationic surfactant, CTAB is easy to be intercalated into interlayer
Table 1
space of expanded vermiculite. The obtained expanded vermi- Thermal properties of CA, MA and SA.
culite/carbon composite was treated with nitric acid (aEVC) to
improve the specific surface area and microporosity of expanded Fatty Melting Latent heats of melting Molar mass
acids temperatures (°C) (J/g) (g/mol)
vermiculite, and then used as capric-myristic-stearic eutectic mix-
ture (CA-MA-SA) supporting matrix. The thermal conductivity and CA 30.51 155.5 172.27
MA 52.32 184.5 228.37
latent heats of the CA-MA-SA/aEVC were both higher than those of SA 67.20 199.1 284.48
CA-MA-SA/EV.
618 H. Wei et al. / Applied Energy 178 (2016) 616–623

Table 2 2.5. Preparation of the composite PCM

The mass ratios and melting temperatures of experimental eutectic mixtures.

Eutectic mixtures Mass ratios Melting temperatures (°C) The composite PCMs were prepared by the vacuum impregna-
CA-MA 74.8:25.2 25.23 tion method. The solid CA-MA-SA eutectic mixture and supporting
CA-SA 95.4:4.6 28.71 matrix were placed in a conical flask with stirrer and the mass
MA-SA 79.8:20.2 45.24 ratio of eutectic and supporting matrix is 2:1. The vacuum pump
CA-MA-SA 72.5:22.5:5.0 23.96 was connected to the conical flask to evacuate air. Then the conical
flask was heated under the vacuum condition in order to melt
solid CA-MA-SA. The supporting matrix was completely sub-
100% MA merged in the liquid of melting CA-MA-SA eutectic to achieve
100 (0)
the adsorption saturation of CA-MA-SA. CA-MA-SA was easily
H
absorbed under the vacuum condition. After vacuum impregna-
90 10 tion, the composite PCM was thermally filtered by filter papers
80 B 20
to remove excess CA-MA-SA at 70 °C until no melted CA-MA-SA
seepage from composites was observed and the mass loss of com-
n%

Ma

70 30
posite PCM was less than 1%.
o

ss
siti

60 40
o

co
mp

mp

50
co

50
o

2.6. Characterization
s it
ss

40
io n

60
Ma

30 70 The phase compositions of the supporting matrices were stud-

E A
20 E' 80 ied by X-ray diffraction (XRD, UltimaIII). The microstructures of
the supporting matrix and composite PCM were observed by scan-
10 90
ning electron microscopy (SEM, SUPRA55). The chemical compati-
100% SA K C D 100%
90 80 70 30 10 100 (0)
CA bility between CA-MA-SA and the supporting matrix was
0 (100) 60 50 40 20
Mass composition %
examined by Fourier transform infrared spectroscopy (FT-IR,
Nicolet-5700). The thermal conductivities of the samples were
Fig. 1. The ternary phase diagram and eutectic point scope of CA-MA-SA. measured by thermal conductivity analyzer (DRL-II) with measure-
ment accuracy within ±3%. Thermal properties of the samples were
measured via differential scanning calorimetry (DSC, Q20) with
0.0 temperature accuracy within ±0.1 °C and enthalpy accuracy within
±1.0%. The tests were measured at a heating rate of 3 °C/min from
-0.5
10 °C to 70 °C. The thermal stabilities of CA-MA-SA and composite
PCM were measured using thermo-gravimetric analysis (TGA, Q50)
-1.0
with temperature accuracy within ±1 °C and weight accuracy
Heat flow (W/g)

-1.5 within ±0.01%. The tests were measured at a heating rate of 5 °C/
min from room temperature to 500 °C.
CA-MA-SA (72.5:22.5:5.0)
-2.0 The thermal cycling test was used to determine the thermal
reliability of the composite PCM. The thermal cycling test was as
-2.5 follows: the composite PCM on a filter paper was placed into a
thermostatic chamber. The composite PCM was heated above the
-3.0
melting temperature and then cooled to room temperature. Thus
-3.5
a thermal cycle, including a melting and freezing process, was
completed. The thermal cycle was repeated 200 times and the filter
0 10 20 30 40 50 paper was substituted per 10 times [23].
Temperature (°C)

Fig. 2. DSC curve of CA-MA-SA at the heating rate of 1 °C/min.

3. Results and discussion

2.4. Preparation of the supporting matrix 3.1. Characterization of the supporting matrix

The expanded vermiculite (EV), expanded vermiculite/carbon The XRD patterns of the EV, OEV, EVC and aEVC are shown in
composite (EVC) and expanded vermiculite/carbon composite with Fig. 4. From the XRD pattern of the EV, the expanded vermiculite
acid treated (aEVC) were used as the supporting matrices in this consists of phlogopite with minor vermiculite and hydrobiotite.
study. The d-spacing between (0 0 1) lattice planes (d001-values) of vermi-
The EVC composite was prepared as follows: the EV was dis- culite and phlogopite are 1.495 nm and 0.996 nm, respectively. For
persed in the CTAB solution (4 wt%) and the mass ratio of EV to the OEV sample, the d001-values of vermiculite and phlogopite are
CTAB is 5:2. Then, the slurry was stirred at 70 °C for 12 h and larger than those of the EV and the peaks decrease in intensity,
standing at room temperature for 12 h. The obtained product which indicate that the exchangeable cations in the EV layers
was dried, ground and named as OEV. Finally, OEV was calcined were changed with the cetyl trimethyl ammonium cations
at 600 °C for 3 h in a reducing atmosphere, and the product was (C16H33(CH3)3N+). From the patterns of the EVC and aEVC, the
named as EVC. Fig. 3 shows the preparation process of EVC. d001-values of phlogopite are close to that of EV, suggesting that
The process of acid treatment for EVC was as follows: the EVC the CTAB in the layer was carbonated in situ [19]. Moreover, the
was dispersed in HNO3 solution (8 mol/L) with a ratio of EVC mass intensity of phlogopite diffraction peak weaken evidently by acid
to volume of HNO3 solution of 1 g/10 ml and stirred at 90 °C for 2 h. treatment, which could be related to the less ordered layered
Then, the sample was filtrated, dried and ground. structure [29].

Fig. 3. Schematic diagram of the preparation process of EVC.
Intensity (a.u.)
P
V
P/H
10 20 30
2 theta/degree
Fig. 4. XRD patterns of EV, OEV, EVC, aEVC.
3.2. Characterization of the composite PCM
The SEM images of EV, EVC, aEVC and CA-MA-SA/aEVC are
shown in Fig. 5. It can be seen from Fig. 5(a) that the EV shows typ-
ical lamellar morphology and consists of thick aggregates of parti-
cles [21,22]. The EVC maintains the lamellar morphology,
suggesting that EV shows no significant change in morphology
after carbonizing [Fig. 5(b)]. According to Fig. 5(c), the aEVC was
partially delaminated to form a highly porous microstructure after
treated with nitric acid. In CA-MA-SA/aEVC composite PCM, the
pores of aEVC are fully filled with CA-MA-SA [Fig. 5(d)].
Moreover, energy spectrum analysis of the EV, EVC and aEVC
which corresponded with the red rectangle in Fig. 5(a), (b), (c)
are given in Table 3. There are significant changes in the elemental
composition after modified treatment for EV. For the EVC and
aEVC, the elemental composition of carbon were confirmed to be
13.9% and 16.2% by weight percentage, suggesting that the CTAB
impregnated with EV have been carbonized. After acid treatment,
the content of interlayer cation (K and Ca) decreased significantly
due to the replacement of interlayer cations by H+. The content
of octahedrally coordinated cations (Mg, Ti and Fe) and tetrahe-
drally coordinated cations (Al) reduced greatly owing to the fact
that the delamination was accompanied by the leaching of most
positive ions in the octahedral and tetrahedrally sheets. Conse-
quently highly porous structure were formed in aEVC to provide
larger space for CA-MA-SA.
H. Wei et al. / Applied Energy 178 (2016) 616–623 619
V-Vermiculite The FT-IR spectra of samples are shown in Fig. 6. As seen
P-Phlogopite
H-Hydrobiotite
from the spectrum of EV, the peaks located at 3464 cm1 and
1634 cm1 are assigned respectively to OH stretching and bending
aEVC vibration of the interlayer water. The characteristic peak of SiAO
stretching vibration is observed at 1012 cm1 and the peak at
440 cm1 is attributed to SiAOASi bending vibration of vermiculite
[30]. In the spectrum of aEVC, the infrared spectra show more sig-
nificant alteration at the region below 1250 cm1. The characteris-
EVC
tic SiAO stretching band shifts from 1012 cm1 to 1077 cm1 and
OEV the SiAOASi bending vibration band shifts from 440 cm1 to
464 cm1. The intensity of the two peaks increase, indicating that
the siloxanes groups become the principal structure frame in the
EV
aEVC. The new peaks near 1228 cm1 and 958 cm1 are respec-
tively attributed to asymmetric stretching vibrations of SiAO and
40 50 stretching vibrations of SiAOH, which confirms the presence of
hydrous amorphous silica in acid-treated samples. The new peak
at 796 cm1 is originated from the bending vibrations of SiO4
tetrahedra, which is similar to that of amorphous silica. On the
basis of the above observations, it is concluded that the acid-
treated EV was essentially delaminated with exposed SiAOH
groups on the surface. Consequently, the adsorptive properties
was enhanced [31].
In the spectrum of CA-MA-SA, peaks at 2928 cm1 and
2842 cm1 are attributed to ACH3 and ACH2 symmetrical stretch-
ing, respectively. The peak at 1705 cm1 is attributed to C@O sym-
metrical stretching vibration. Peaks at 1464 cm1 and 1291 cm1
correspond to the out-of-plane bending vibration of the AOH func-
tional group, and 937 cm1 corresponds to the out-of-plane bend-
ing vibration of the OH functional group [32,33]. The peak at
724 cm1 is attributed to the swinging vibration of AOH functional
group. Obviously, the characteristic peaks of supporting matrix and
CA-MA-SA can be observed in the spectrum of CA-MA-SA/aEVC
composite PCM and no additional bands appear. Therefore, there
is no chemical reaction between the CA-MA-SA and supporting
matrix. Specially, the peaks at 3464 cm1 and 1634 cm1 in the
spectrum of aEVC weaken evidently in the spectrum of CA-MA-
SA/aEVC due to the formation of hydrogen bond formed by hydro-
gen of carbon chain of CA-MA-SA and supporting matrix [33]. The
hydrogen bond is of benefit to preventing the leakage of melted
CA-MA-SA from the supporting matrix due to the fact that the force
of hydrogen bond is much stronger than that of Van der Waals.
Compared with the spectrum of CA-MA-SA/aEVC before thermal
cycling, the peak positions and shapes are almost unchanged in
the spectrum of CA-MA-SA/aEVC after thermal cycling. The results
suggest that the chemical structure of the composite PCM is not
620 H. Wei et al. / Applied Energy 178 (2016) 616–623

Fig. 5. SEM images of the (a) EV, (b) EVC, (c) aEVC and (d) CA-MA-SA/aEVC.

Table 3
The main elemental composition of EV, EVC and aEVC.
CA-MA-SA/aEVC
Element EV (wt%) EVC (wt%) aEVC (wt%) after thermal cycling
C – 13.9 16.2
O 64.4 55.4 59.4
Mg 5.2 6.1 0.9
Al 6.6 5.9 1.0
CA-MA-SA/aEVC
Si 13.8 11.4 21.6
K 2.7 1.9 0.4
before thermal cycling
Ca 0.6 0.4 0.2
Ti 0.7 0.5 0.2
Fe 6.0 4.5 0.1
Transmittance (%)

Total 100.0 100.0 100.0

CA-MA-SA

1291 724
damaged during the thermal cycling. Therefore, the prepared com- 2842 1705 937
2928 1464
posite PCMs have good chemical compatibility.
aEVC
3.3. Thermal properties of the composite PCMs
796
The DSC curves of the CA-MA-SA and the composite PCMs are 1228 958 464
shown in Fig. 7. Thermal properties of the CA-MA-SA and compos- EV 1077
ite PCMs are given in Table 4. As seen from the table, the melting
temperature are 23.96 °C, 23.26 °C, 23.21 °C and 22.92 °C for CA- 3464 1634
MA-SA, CA-MA-SA/EV, CA-MA-SA/EVC and CA-MA-SA/aEVC, 1012 440
respectively. The freezing temperature are 21.83 °C, 21.62 °C,
20.54 °C and 21.03 °C, respectively. The slight decrease in phase 4000 3500 3000 2500 2000 1500 1000 500
change temperature is due to the weak attractive interaction Wavenumber (cm ) -1

between CA-MA-SA molecules and inner surface wall of the porous

supporting matrices [22]. Fig. 6. FTIR spectra of EV, aEVC, CA-MA-SA, CA-MA-SA/aEVC composite before and
Moreover, the latent heat of melting is 86.4 J/g for CA-MA-SA/ after thermal cycling.
aEVC, which is 39.1% and 83.0% higher than that of CA-MA-SA/EV
and CA-MA-SA/EVC, respectively. Similarly, the CA-MA-SA/aEVC
nated, corroded and chemically functionalized, and the SiAOH
has the highest latent heat of freezing among the composite PCMs.
groups are increasing within the EVC surface [34]. Consequently,
The latent heats of CA-MA-SA/EVC decrease compared with those
the adsorption property is greatly enhanced by acid treatment.
of CA-MA-SA/EV. The reason is that the latent heats of composite
PCMs are largely determined by the adsorbed amounts of CA-
MA-SA. The carbon in the layers of the EV occupied some layer 3.4. Thermal reliability of the composite PCM
space and resulted in reducing the absorbed amount of CA-MA-
SA. The increase of the latent heats of CA-MA-SA/aEVC is attributed The composite PCM should have stable thermal properties and
to the fact that the EVC with acid treatment is essentially delami- stable chemical structure. Fig. 8 shows the DSC curves of the
 H. Wei et al. / Applied Energy 178 (2016) 616–623 621

6 from 86.4 J/g and 80.4 J/g to 80.5 J/g and 78.6 J/g, respectively. The
melting and freezing temperature and latent heats of the compos-
ite PCM after thermal cycling changed slightly in a reasonable
4 level. Therefore, the prepared CA-MA-SA/aEVC composite PCM
CA-MA-SA has good thermal reliability after thermal cycling.
CA-MA-SA/EV The thermo-gravimetric analysis (TGA) was also employed to
Heat flow (W/g)

2 CA-MA-SA/aEVC evaluate thermal stability of the prepared composite PCM. Fig. 9

CA-MA-SA/EVC shows the TGA curves of pristine CA-MA-SA and CA-MA-SA/aEVC
0 composite PCM up to 500 °C. For the CA-MA-SA/aEVC, there was
small mass loss (5.2%) below 200 °C, which means that the CA-
MA-SA/aEVC had a good thermal stability in the working temper-
CA-MA-SA/EV
-2 ature range which is always designed as below 60 °C. The total
CA-MA-SA/aEVC
mass loss of CA-MA-SA and CA-MA-SA/aEVC composite PCM were
about 99.6% and 55.8%, respectively. The observed weight loss was
-4 ascribed to the decomposition of CA-MA-SA. Moreover, the onset
10 20 30 40
decomposition temperature of CA-MA-SA/aEVC has been post-
Temperature (°C) poned compared with the pristine CA-MA-SA. The decomposition
process of CA-MA-SA/aEVC has been prolonged from 291.8 °C to
Fig. 7. DSC curves of the CA-MA-SA and the composite PCMs.
336.1 °C. These results mean that the decomposition of CA-MA-
SA was retarded in the CA-MA-SA/aEVC composite PCM and the
working thermal stability of CA-MA-SA/aEVC composite PCM was
Table 4
Thermal properties of CA-MA-SA and the composite PCM.
enhanced.

Samples Melting Latent Freezing Latent

temperature heat of temperature heat of
3.5. Thermal conductivity of the composite PCM
(°C) melting (°C) freezing
(J/g) (J/g) The thermal conductivity of supporting matrices and composite
CA-MA-SA 23.96 158.7 21.83 154.3 PCMs are shown in Fig. 10. The thermal conductivity of EV, EVC and
CA-MA-SA/EV 23.26 62.1 21.62 57.7 aEVC is 0.403 W/mK, 0.572 W/mK and 0.539 W/mK, respectively.
CA-MA-SA/EVC 23.21 47.2 20.54 42.9 The EV matrix is largely composed of phlogopite and its thermal
CA-MA-SA/aEVC 22.92 86.4 21.03 80.4
conductivity is close to the reported value of phlogopite (0.44 W/
mK) [35]. The thermal conductivity of aEVC was obviously
enhanced due to implanting carbon with high thermal conductiv-
ity [36]. The slight decrease of the thermal conductivity of aEVC
2.0
is attributed to the increased defects caused by acid treatment.
The thermal conductivity of inorganic materials is governed by
1.5
phonon propagation [33]. The increased defects caused by acid
treatment can lead to the scattering of phonons, which causes
1.0
the decrease of thermal conductivity. As shown in Fig. 10, the ther-
Heat flow (W/g)

0.5 mal conductivity of composite PCM is higher than that of corre-

sponding supporting matrix due to that the air was replaced by
0.0 CA-MA-SA in the composite PCM, and the thermal conductivity
of CA-MA-SA (around 0.2–0.3 W/mK) is higher than that of air
-0.5 (around 0.02 W/mK). The thermal conductivity of CA-MA-SA/EVC
before thermal cycles (0.693 W/mK) and CA-MA-SA/aEVC (0.667 W/mK) composite
-1.0 after thermal cycles PCMs are 36.7% and 31.6% higher than that of CA-MA-SA/EV,
respectively.
-1.5
10 20 30 40
Temperature (°C)
100
Fig. 8. DSC curves of the CA-MA-SA/aEVC before and after thermal 200 cycles.

80
55.8%
CA-MA-SA/aEVC before and after 200 thermal cycles. The thermal
characteristics of CA-MA-SA/aEVC are given in Table 5. The melting 60
Weight (%)

and freezing temperatures of CA-MA-SA/aEVC before thermal 99.6% CA-MA-SA/aEVC

cycles are 22.92 °C, 21.03 °C, and after thermal cycles 23.56 °C, 40 336.1 °C
21.30 °C, respectively. The latent heats of melting and freezing vary
20

Table 5 CA-MA-SA
Thermal characteristics of CA-MA-SA/aEVC before and after thermal cycling. 0
291.8°C
Cycling Melting Latent heat of Freezing Latent heat of
numbers temperature melting (J/g) temperature freezing (J/g)
(°C) (°C) 100 200 300 400 500

0 22.92 86.4 21.03 80.4

Temperature (°C)
200 23.56 80.5 21.30 78.6
Fig. 9. TGA curves of pristine CA-MA-SA and CA-MA-SA/aEVC composite PCM.
622 H. Wei et al. / Applied Energy 178 (2016) 616–623

the building energy efficiency applications due to its proper phase

0.8 PCM: CA-MA-SA
change temperature range, relatively high latent heat and thermal
0.7 0.693 conductivity, good thermal reliability and chemical stability.
0.667
Thermal conductivity (W/mK)

0.6 0.572
0.539 References
0.507
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